Issue 32, 2024

Understanding and tuning the electronic structure of pentalenides

Abstract

Here we report the first example of systematic tuning of the electronic properties of dianionic pentalenides through a straightforward synthetic protocol which allows the controlled variation of substituents in the 1,3,4,6-positions to produce nine new compounds, representing the largest pentalenide study to date. Both electron-withdrawing as well as electron-donating aromatics have been incorporated to achieve different polarisations of the bicyclic 10π aromatic core as indicated by characteristic 1H and 13C NMR shifts and evaluated by DFT calculations including nucleus-independent chemical shift (NICS) scans, anisotropy of the induced current density (ACID) calculations, and natural bond orbital (NBO) charge distribution analysis. The introduction of methyl substituents to the pentalenide core required positional control in the dihydropentalene precursor to avoid exocyclic deprotonation during the metalation. Frontier orbital analyses showed arylated pentalenides to be slightly weaker donors but much better acceptor ligands than unsubstituted pentalenide. The coordination chemistry potential of our new ligands has been exemplified by the straightforward synthesis of a polarised anti-dirhodium(I) complex.

Graphical abstract: Understanding and tuning the electronic structure of pentalenides

Supplementary files

Article information

Article type
Edge Article
Submitted
01 9 2023
Accepted
01 7 2024
First published
05 7 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 12765-12779

Understanding and tuning the electronic structure of pentalenides

N. A. Jenek, A. Helbig, S. M. Boyt, M. Kaur, H. J. Sanderson, S. B. Reeksting, G. Kociok-Köhn, H. Helten and U. Hintermair, Chem. Sci., 2024, 15, 12765 DOI: 10.1039/D3SC04622B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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